WO2006057374A1 - Procede de preparation de particules fines composites - Google Patents

Procede de preparation de particules fines composites Download PDF

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Publication number
WO2006057374A1
WO2006057374A1 PCT/JP2005/021753 JP2005021753W WO2006057374A1 WO 2006057374 A1 WO2006057374 A1 WO 2006057374A1 JP 2005021753 W JP2005021753 W JP 2005021753W WO 2006057374 A1 WO2006057374 A1 WO 2006057374A1
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WIPO (PCT)
Prior art keywords
pressure
fine particles
composite fine
polymer material
solvent
Prior art date
Application number
PCT/JP2005/021753
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English (en)
Japanese (ja)
Inventor
Kenji Mishima
Kiyoshi Matsuyama
Original Assignee
Japan Science And Technology Agency
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Filing date
Publication date
Application filed by Japan Science And Technology Agency filed Critical Japan Science And Technology Agency
Priority to JP2006547886A priority Critical patent/JPWO2006057374A1/ja
Priority to EP05809275A priority patent/EP1842586A1/fr
Priority to US11/791,578 priority patent/US20080274275A1/en
Priority to AU2005308133A priority patent/AU2005308133B2/en
Publication of WO2006057374A1 publication Critical patent/WO2006057374A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/43—Mixing liquids with liquids; Emulsifying using driven stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/49—Mixing systems, i.e. flow charts or diagrams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/501—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0404—Technical information in relation with mixing theories or general explanations of phenomena associated with mixing or generalizations of a concept by comparison of equivalent methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/04—Specific aggregation state of one or more of the phases to be mixed
    • B01F23/043—Mixing fluids or with fluids in a supercritical state, in supercritical conditions or variable density fluids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing composite fine particles of a polymer material and a core substance. More specifically, the present invention relates to a method for producing fine composite particles having a uniform size on the order of several microns to nanometers. Background art
  • Dispersion polymerization and emulsion polymerization using surfactants and emulsifiers are used for the production of polymer fine particles and microcapsules encapsulating core materials such as inorganic particles (Japanese Patent Laid-Open No. Sho 5-6-7 6 4 4 7). No. publication).
  • core materials such as inorganic particles
  • a method for producing polymer fine particles using a high-pressure fluid such as supercritical carbon dioxide has been developed (see Japanese Patent Application Laid-Open No.
  • coated fine particles can be produced by dissolving the above-described substances in a high-pressure fluid containing a supercritical fluid and an additive solvent, and rapidly expanding the mixture into the atmosphere.
  • the present invention provides a method for producing composite fine particles of a polymer material and a core substance having a size of several micrometers or less, more preferably a size of nanometer order (size of ⁇ ⁇ or less). Objective.
  • the present invention provides a method for producing composite fine particles of a polymer material and a core substance, and the method comprises a high pressure containing a supercritical fluid and an additive solvent due to a shear stress of 1 Pa or more. Dissolving and dispersing a polymer material and a core substance in the fluid, respectively; and ejecting a high-pressure fluid containing the polymer material and the core substance into a poor solvent to rapidly expand the fluid.
  • the dissolving and dispersing steps are performed using a high speed stirrer equipped with a mechanical seal. :
  • the core material is dispersed using a shear stress of 1 Pa or more.
  • the core substance is coated with the polymer material.
  • the core material is an inorganic particle.
  • the supercritical fluid is selected from the group consisting of carbon dioxide, ammonia, methane, ethane, ethylene, butane, and propane
  • the additive solvent is water, methanol, ethanol, propanol, acetone, and At least one selected from the group consisting of these mixtures
  • the poor solvent is at least one selected from the group consisting of water, methanol, ethanol, propanol, acetone, liquid nitrogen, and mixtures thereof. It is a seed.
  • a high-speed stirring device is used for a high-pressure fluid containing supercritical carbon dioxide or the like! / After dissolving and dispersing the polymer material and the core substance, respectively, and rapidly expanding, composite particles of the polymer material and the core substance having a size of several micrometers or less, preferably a nanometer order size, are obtained. Can be manufactured. Various composite fine particles can be produced by combining various polymer materials and core materials in consideration of solubility in a high-pressure fluid.
  • the core material is dispersed in the polymer material (that is, the core material is Obtaining composite fine particles coated with polymer material be able to.
  • FIG. 1 is a schematic view of an apparatus used in the method for producing composite fine particles of the present invention.
  • FIG. 2 is a scanning electron micrograph of the polylactic acid titanium monoxide composite fine particles produced by the method of the present invention (Example 1).
  • FIG. 3 is a transmission electron micrograph of polylactic acid titanium monoxide composite fine particles produced by the method of the present invention (Example 1).
  • FIG. 4 is a particle size distribution diagram of the polylactic acid-titanium oxide composite fine particles obtained by the method of the present invention (shear stress: 5 Pa) (Example 2).
  • FIG. 5 is a particle size distribution diagram of the polylactic acid titanium monoxide composite fine particles obtained at a slow stirring speed (shear stress: 0.0 0 1 Pa) (Comparative Example 1).
  • Fig. 6 shows the relationship between the analysis results of the polylactic acid titanium monoxide composite particles produced by the method of the present invention using an X-ray diffraction apparatus (strength of rutile-type titanium oxide at 27 °) and the shear stress due to stirring. It is a graph which shows.
  • FIG. 7 is a schematic diagram for explaining the shear stress. BEST MODE FOR CARRYING OUT THE INVENTION
  • a high-pressure fluid containing a supercritical fluid and an added solvent is dissolved and a core substance is dispersed in a high-pressure fluid containing a supercritical fluid and an added solvent by a shear stress of 1 Pa or more. Squirting into a solvent and rapidly expanding.
  • a high-speed agitator is used to disperse the core substance into fine particles having a nanometer order size in a high-pressure fluid and rapidly expand, thereby dissolving the polymer material in the high-pressure fluid.
  • composite particles of the core material can be precipitated.
  • the core material can be highly dispersed by supersaturating the polymer material dissolved around the dispersed core material fine particles.
  • Composite fine particles coated with a child material that is, a core material coated with a polymer material are produced.
  • the composite fine particles refer to particles composed of a polymer material and a core substance and having a size of 10 ⁇ m or less, preferably a size of several nm or less.
  • the composite fine particles include composite fine particles in which a core substance is dispersed in a polymer material, that is, composite fine particles in which a core substance is coated (coated) with a polymer material.
  • the “supercritical fluid” refers to a fluid under a temperature and a pressure exceeding a critical temperature and a critical pressure, but may include a subcritical fluid.
  • the chemical species of such a supercritical fluid is not particularly limited.
  • an organic gas that is in a gaseous state at room temperature can be used.
  • Carbon dioxide, carbon monoxide, ammonia, methane, ethane, propane, ethylene, butane and the like are preferable, carbon dioxide, ammonia, methane, ethane, ethylene and butane are more preferable, and carbon dioxide and ethylene are more preferable.
  • the “added solvent” refers to a solvent added for the purpose of enhancing the solubility of a polymer material that coats the target composite fine particle core material in a high-pressure fluid. Usually, it is selected from the poor solvent for the polymer used (detailed below). For example, in the case of a fluid that is not a high-pressure fluid (for example, a fluid under pressure during a rapid expansion process, a fluid under normal pressure, etc.), it is desirable that the solubility of the high-molecular material is low or extremely low.
  • Such an additive solvent may be a solvent in a gas state or a liquid state at room temperature.
  • low molecular weight chemicals such as carbon dioxide, methane, ethane, ethylene, propane, pentane, acetic acid, water, methanol, ethanol, and ammonia are suitable.
  • water, methanol, ethanol, propanol, acetone, and a mixture thereof are more preferable.
  • the “poor solvent” refers to a solvent having an extremely low power solubility having the ability to dissolve a polymer material. Therefore, the poor solvent is appropriately selected according to the type of polymer material to be used.
  • a poor solvent a polar solvent is preferable, and a solvent in a liquid state at room temperature is more preferable.
  • liquid nitrogen can be used.
  • the additive solvent and the poor solvent used in the method of the present invention may be the same or different.
  • the “high pressure fluid” refers to a fluid under supercritical to critical pressure, and in the present invention, particularly refers to a fluid containing a supercritical fluid and an additive solvent.
  • the high-pressure fluid is usually in a gaseous state, but may contain a liquid state substance.
  • the “polymer material” refers to a material used as a raw material for coating the target composite fine particles.
  • the polymer material department is not particularly limited, and examples thereof include the following materials: polyamide (nylon 6, nylon 6-6, etc.), polyethylene, polypropylene, polypten, polyethylene dallicol, polypropylene glycol, polybulu alcohol, polyacryl Amides, Atalyl oils (polyacrylic acid; polyacrylic esters such as polymethyl methacrylate), phenolic resins, epoxy resins, silicone resins, polyurethanes, polyesters, polybutadienes, polystyrenes, polytetrafluoroethylene, 'polylactic acid, polycarbonates, polyacetals, Loxane, dextran, gelatin, starch, cellulose (cellulose butyrate , Nitrocellulose, etc.), saccharides, chitins, polypeptides, and high molecular copolymers containing them as a constituent, and mixtures containing them.
  • the core substance refers to a substance that can be coated with a polymer material to form composite fine particles, and can be an organic substance or an inorganic substance that is insoluble in a high-pressure fluid.
  • the core material is selected according to the application of the composite fine particles. Examples include pharmaceuticals, food additives, materials used for copying, recording and display, and materials used as materials for electronic devices and fuel cells. It is done.
  • organic substances suitable as the core substance include proteins (for example, tuberactinomycin, polymyxin, insulin, lysozyme, CK-chymolipsin, pepsin, ovalbumin, serum albumin, amylase, lipase, casein, etc.) Dyes and paints (for example, oral dyes, shellac, maleic resins, acrylic resins, carbon black, etc.).
  • proteins for example, tuberactinomycin, polymyxin, insulin, lysozyme, CK-chymolipsin, pepsin, ovalbumin, serum albumin, amylase, lipase, casein, etc.
  • Dyes and paints for example, oral dyes, shellac, maleic resins, acrylic resins, carbon black, etc.
  • any inorganic substance such as sulfides, silicon compounds, metals, metal compounds, alkali metal compounds, and alkaline earth compounds known to those skilled in the art such as the electronic equipment field can be used.
  • inorganic substances include the following substances: sulfides (for example, zinc sulfide, cadmium sulfide, sodium sulfide, etc.); silicon compounds (for example, silicon dioxide); metals (for example, iron) , Nickel, cobalt, stainless steel, iron, zinc, etc.); oxides (eg, iron oxide, titanium oxide, tungsten oxide, nickel oxide, hydroxide, molybdenum oxide, manganese oxide, copper oxide, tartan oxide) ; metal compounds (e.g., ferrite, MnF e 2 ⁇ 4, MnF e 2 0 4, ZnFe 2 ⁇ 4 and N i Fe 2 0 4, CuF e 2 ⁇ 4); carbides (P d_c, platinum-supported carbon P t — C) etc.
  • sulfides for example, zinc sulfide, cadmium sulfide, sodium sulfide, etc.
  • silicon compounds for example, silicon dioxide
  • metals for example
  • shearing is applied to the polymer material and the core substance in a high-pressure fluid.
  • a stirrer that can stir at high speed.
  • the high-speed stirring device is not particularly limited as long as it is provided in a high-pressure vessel and can stably disperse the core substance to a size of several / zm or less, preferably a nanometer order size.
  • the stirrer include a stirrer equipped with a mechanical seal.
  • the conventional magnetic induction stirrer is stable because, when high-speed stirring of several thousand rpm is performed, an electromagnetic induction heating phenomenon is generated by the magnet installed in the stirrer and heat is generated. In many cases, proper stirring becomes difficult.
  • a stirring device equipped with a mechanical seal by employing a stirring device equipped with a mechanical seal, a high speed of 5, OOO rpm or more, preferably 10, OOO rpm or more, more preferably 15,000 rpm or more. Stirring can be performed in a stable state.
  • a shear stress of 1 Pa or more can be applied to the high-pressure fluid existing between the stirring blade and the wall of the stirring vessel, and the core material particles are several zm or less.
  • it is dispersed in a high-pressure fluid with a size of nanometer order.
  • the core material is dispersed using a shearing stress of 1 Pa or more generated between the stirring blade and the wall of the stirring vessel.
  • the distance between the stirring blade and the stirring vessel wall surface is 0.5 to L: 0 mm, more preferably 1 to 5 mm.
  • the core material which is a nanoparticle that easily aggregates in a high-pressure fluid, is prevented from agglomerating, and the microparticles are dispersed and used for the next rapid expansion process.
  • Composite fine particles can be produced.
  • the high-speed stirring apparatus is stirred under a shear stress of 1 Pa or more.
  • the shear stress generated by the stirrer is calculated as follows.
  • the frictional force can be expressed by the product of the shear stress ⁇ (frictional force per unit surface area) and the area of the flat plate ⁇ 4, as expressed by the following equation (2).
  • the speed (m / sec) is determined by the rotation speed of the apparatus and the diameter of the stirring cylinder.
  • the circumference of the stirring cylinder is
  • a polymer material is dissolved and a core substance is dispersed in a high-pressure fluid containing a supercritical fluid and an additive solvent while stirring under a shear stress of 1 Pa or more.
  • the order of mixing the supercritical fluid, the added calo solvent, the polymer material, and the core substance is not particularly limited.
  • a fluid containing a supercritical fluid and an additive solvent may be prepared in advance, and the polymer material may be dissolved and the core substance dispersed therein.
  • a supercritical fluid is further added to the polymer material. May be dissolved and the core material may be dispersed.
  • the polymer material and the core material may be previously dissolved and dispersed in a small amount of an additive solvent, respectively.
  • the core substance is added at a ratio of about 0.1 to 1 part by mass, preferably about 0.1 to 1 part by mass, with respect to 1 part by mass of the polymer material.
  • the supercritical fluid is used at a ratio of about 20 to 100 parts by mass, preferably about 30 to 80 parts by mass, with respect to 1 part by mass of the polymer material.
  • the additive solvent is used in a ratio of about 1 to 100 parts by mass, preferably about 10 to 50 parts by mass with respect to 1 part by mass of the polymer material.
  • the pressure in this step is preferably 7.2 to 3 OMPa, more preferably 15 to 25 MPa.
  • the temperature is preferably 2 7 3 to 3 5 3 K, more preferably 2 98 to 3 13 K.
  • a high-pressure fluid containing a polymer material and a core substance is stirred using a high-speed stirring device equipped with a mechanical seal at the above critical temperature and critical pressure.
  • Such high-speed stirring is performed under a shearing stress of 1 Pa or more, preferably 2 Pa or more, more preferably 5 Pa or more.
  • a high-pressure fluid containing the dissolved polymer material and the dispersed core substance is ejected into the poor solvent and rapidly expanded.
  • the means for ejecting the high-pressure fluid into the poor solvent is not particularly limited.
  • a means for ejecting a high-pressure fluid under a high-pressure state into a poor solvent using a nozzle or the like; a means for previously dissolving a surfactant or the like in the poor solvent and blowing a high-pressure fluid may be used.
  • the dispersibility of the composite fine particles can be further improved by appropriately changing the type, pressure, temperature, etc. of the poor solvent in consideration of the high molecular material used and the solubility of the core substance.
  • the temperature of the poor solvent is preferably 2 73 to 3 53 K, more preferably 2 98 to 3 13 K.
  • a means for rapidly stirring a high-pressure fluid for example, a high-speed stirring apparatus equipped with a mechanical seal
  • a high-pressure fluid for example, a high-speed stirring apparatus equipped with a mechanical seal
  • a high-pressure fluid for example, a high-speed stirring apparatus equipped with a mechanical seal
  • a high-pressure fluid for example, a high-speed stirring apparatus equipped with a mechanical seal
  • a high-pressure fluid are ejected into a poor solvent and rapidly expanded.
  • the apparatus is equipped with means (for example, a nozzle).
  • an apparatus as shown in Fig. 1 can be used.
  • the method for producing composite fine particles of the present invention will be described more specifically based on FIG.
  • the equipment shown in Fig. 1 is a pressurizing section from cylinder 1 to stop pulp V-2, a mixing section from downstream to stop pulp V-5, and a poor solvent for rapidly expanding and dispersing fine particles. It is comprised from the particle
  • the pressure booster is mainly a cylinder for supplying supercritical fluid (for example, carbon dioxide).
  • a drying pipe 2, a cooling unit 3, and a filter 4 are provided between a cylinder 1 filled with liquid carbon dioxide and a booster pump 5.
  • the liquid carbon dioxide from the cylinder 1 passes through the drying pipe 2, the cooling unit 3, and the filter 4 and is pressurized by the booster pump 5 and sent to the mixing section.
  • the drying tube 2 is filled with a desiccant and removes water from the liquid carbon dioxide that passes through it.
  • the drying pipe 2 is a carrier gas drying pipe (Gas D riers; material SUS 3 16; maximum working pressure 2 OMPa, inner diameter 35.5) manufactured by GL Sciences Inc. mm, length 3 10 mm), and molecular sieve 5 A (1/16 inch pellet) manufactured by GL Sciences Inc. is used as the desiccant.
  • the cooling unit 3 is filled with, for example, ethylene glycol, and the ethylene glycol is configured to be cooled to about 2600 K.
  • the liquid carbon dioxide from which moisture has been removed by the drying tube 2 is cooled by this ethylene glycol.
  • the cooling unit 3 is used. And using Yamato Scientific BL-22.
  • a filter 4 is provided after the cooling unit 3. This filter 4 removes impurities such as dust and prevents impurities from entering the booster pump 5.
  • a filter (FT 4-10, manufactured by GL Sciences Inc.) having an average pore diameter of about 1 ⁇ is used as the filter 4.
  • the booster pump 5 is a single plunger pump for high pressure manufactured by GL Sciences Inc. AP S— 5 L (maximum pressure 58.8 MPa, normal pressure 49. OMP a, 3 ⁇ 43 ⁇ 4 * 0.5 to 5.2 m 1 min) is used. A cooler is attached to the head portion of the booster pump 5 to prevent vaporization of liquid carbon dioxide.
  • a pressure control valve V-1 is provided in the pressurizing unit, and the pressure in the system of the pressurizing unit and mixing unit is set to an arbitrary pressure by the pressure control valve V-1.
  • TESCOM made 2 6 — 1 721-24 is used as the pressure control valve V-1.
  • This pressure control valve V-1 has a pressure of ⁇ 0.
  • the pressure in the system can be controlled with an accuracy within IMP a, and the maximum operating pressure is 41.5 MPa o
  • a pressure gauge 6 is provided in the pressure raising unit, and the pressure in the system is measured by the pressure gauge 6.
  • the pressure gauge 6 is provided with an upper limit contact output terminal, which is set to turn off the booster pump 5 at the specified pressure.
  • a pressure gauge In the examples described below, a pressure gauge
  • an additive solvent tank when an additive solvent tank is provided, a booster pump, a check valve, and a stop pulp are arranged between the additive solvent tank and the high pressure cell 10. Placed.
  • the additive solvent (ethanol) filled in the additive solvent tank passes through the check valve by the booster pump, is supplied into the high-pressure cell 10, and is mixed with carbon dioxide supplied from the cylinder 1.
  • the additive solvent may be mixed with the supercritical fluid in advance, or may be supplied together with the polymer material into the high-pressure cell 10 of the mixing unit described in detail below.
  • a stop pulp V-2 is arranged between the pressurizing unit and the mixing unit, and the outflow of fluid in the mixing unit can be controlled by the stop pulp V-2.
  • 2 Way Val O 2 01 20 maximum operating pressure 98.0 MPa manufactured by GL Sciences Inc. is used as the stop valve V-2.
  • a safety valve 7 is provided between the pressurizing unit and the mixing unit to ensure safety.
  • a spring-type safety valve made by NUP RO was used as the safety valve 7, and a stainless steel pipe was used for the piping.
  • the mixing part is mainly composed of a constant temperature water tank 12, and a high pressure cell 10 provided with a preheating pipe 8, a check valve 9 and a high-speed stirring device 11 disposed therein.
  • the constant temperature bath 1 2 is configured to control the temperature of the high pressure cell 10 disposed inside.
  • the temperature control is performed using a temperature controller DB 1000 manufactured by Chinoichi Co., Ltd. This temperature controller
  • a mixture of a supercritical fluid (for example, carbon dioxide) and an additive solvent (for example, ethanol) supplied from the pressurizing unit is sent to the preheating tube 8 and heated from below the critical temperature to above the critical temperature, Supercritical fluid (fluid above critical temperature). This mixture is then adjusted to stop pulp V-3 and V-4 Thus, the high pressure cell 10 is introduced.
  • a check valve 9 is arranged between the preheating column 8 and the stop valves V-3 and V-4.
  • AK I CO SS-53 F4 Maximum operating pressure 34.3 MPa is used as the check valve 9.
  • a quick open / close extraction cell made of AK I CO (material SUS 316, design pressure 39.2 MPa (40 0 kg / cm 2)), design temperature 423. 15 K (150 ° C), ID 55 mm, height 1 10 mm, internal volume 25 Oml).
  • the high-pressure cell 10 is usually charged with a polymer material and a core substance in advance. If necessary, the additive solvent may be added in advance. A supercritical fluid is added to these mixtures, and the high-pressure fluid is stirred at high speed using the high-speed stirring device 11 sealed with the mechanical seal 19.
  • the stirring speed is usually 5000 to 15000 rpm, and the number of rotations of the stirring shaft is displayed by, for example, a digital rotation indicator.
  • 45 40_B 023R4 sp manufactured by Tanken Seal Seiko Co., Ltd. was used as a high-speed stirring device 11 equipped with a mechanical seal.
  • the pressure in the high pressure cell 10 is measured by a Bourdon type pressure gauge E 930 04 6 B (maximum pressure 49. OMP a) manufactured by Yamazaki Keiki Seisakusho (not shown).
  • the pressure gauge PE-33-A strain gauge type, accuracy ⁇ 0.3% FS, FS: kgf / cm 2 ) is used for the calibration of this pressure gauge.
  • a safety valve 14 can be installed above the high-pressure cell 10 in order to prevent an explosion due to a pressure increase in the high-pressure cell 10.
  • the safety valve 14 is made by NUPRO (spring type, 1 77—R3AK I—G).
  • the particle dispersion part following the mixing part includes a poor solvent cell 21 containing a poor solvent and a pressure buffering cell 22 in an air thermostat 18.
  • Dissolve polymer material and core High pressure fluid containing dispersed quality through the protective tube 1 5 through pulp V- 5, the nozzle 17 forces et al, the installed anti-solvent in the air thermostatic chamber 18 (e.g., water) to the poor solvent medium cell 21 comprising Sprayed and dispersed in poor solvent.
  • Excess pressure generated in the anti-solvent cell 21 can be buffered by a pressure relief cell 22 that communicates via a stop valve V-6.
  • the poor solvent cell 21 and the pressure buffering cell 22 are each provided with a heater.
  • the protective tube 15 and the nozzle 17 are also provided with heaters in order to prevent the condensation of the sample due to decompression and the generation of dry ice due to the supercritical fluid (carbon dioxide).
  • the cell made by GL Sciences Co., Ltd. (SUS 316, design pressure 34.3 MPa, design temperature 373. 15 K is used as the poor solvent cell 21 and the pressure buffer cell 22. (100 ° C), inner diameter 45 mm, height 161.5 mm, inner volume 250 m 1) were used.
  • the protective tube 19 was a 1/8 inch stainless steel tube (SUS 3 16, outer diameter 3.1 75 mm, inner diameter 2. 17 mm, length approximately lm).
  • the internal volume of the air temperature chamber 23 is 1 25 dm 3 , and the temperature inside the temperature chamber is controlled at 0.05 ° C by the temperature controller DB 1000 manufactured by Chinoichi Co., Ltd.
  • the nozzle 20 a spray nozzle made by Spraying Systems Japan Co., Ltd. (orifice diameter 0.28 mm, maximum working pressure 280 kg cm 2 ) was used.
  • composite particles made of polyoxylactic acid-coated titanium titanate were produced as follows.
  • the obtained composite fine particles were transferred to a scanning electron microscope (SEM—EDX) S SX—550 manufactured by Shimadzu Corporation, and a transmission electron microscope manufactured by Hitachi, Ltd.
  • Fig. 2 shows a scanning electron micrograph
  • Fig. 3 shows a transmission electron micrograph.
  • a large number of polylactic acid microparticles having a diameter of several ⁇ were obtained.
  • the titanium oxide particles were present in a dispersed state in the resulting polylactic acid fine particles. That is, titanium oxide was coated with polylactic acid.
  • polylactic acid titanium monoxide Composite fine particles were produced.
  • the particle size distribution was measured with a particle size distribution measuring device (Microtrack manufactured by Nikkiso Co., Ltd.). The results are shown in Fig. 4.
  • the obtained composite fine particles showed a normal distribution having a peak particle size of about 4 / zm, and it was found that composite fine particles having a uniform average particle diameter were obtained.
  • Titanium oxide with an average primary particle size of 10 ⁇ nm was used, the pressure in the high-pressure cell 10 was 2 OMPa, the rotational speed of the stirrer was 1,000 rpm, and the shear stress was 0.001 Pa Except that, polylactic acid-titanium oxide composite fine particles were produced in the same manner as in Example 1 above.
  • the particle size distribution was measured with a particle size distribution measuring device (Microtrack manufactured by Nikkiso Co., Ltd.) in the same manner as in Example 2 above. The results are shown in FIG.
  • the composite fine particles obtained when the stirring speed was low (1,000 rpm) showed a polydisperse type particle size distribution. This is thought to be due to insufficient dispersion of the titanium oxide particles. (Example 3)
  • Polylactic acid monotitanate titanium composite particles were produced in the same manner as in Example 1 except that the shear stress was changed from 0 to 2 O Pa.
  • the amount of titanium oxide contained in the obtained composite particles was observed using an X-ray diffraction apparatus (1980 XHF—SRA manufactured by Mac'Sence Co., Ltd.).
  • XHF—SRA X-ray diffraction apparatus
  • the strength of rutile-type oxytitanium at 27 ° increases.
  • FIG. 6 As shown in Fig. 6, as the shearing stress increases with increasing stirring speed, the strength of rutile titanium oxide at 27 ° increases, and the content of titanium oxide in the composite particles also increases. I found out.
  • composite fine particles of a polymer material having a uniform average particle diameter and a core substance having a size on the order of nanometers can be obtained.
  • various composite fine particles in which the core material is coated with the polymer that is, the surface of the core material is coated
  • Such composite fine particles of a polymer single-core material having a size of nanometer order are used in various applications, for example, food, pharmaceuticals, cosmetics, fine particles, depending on the properties and functions of each of the polymer and the core material. It can be used as a catalyst carrier for image elements, toners, paints, fuel cells, etc., and as a carrier for fillers in separation columns for liquid chromatography.

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Abstract

L’invention concerne un procédé de préparation de particules fines composites à partir d’un matériau polymère et d’une substance de noyau, comprenant une étape de dissolution et de dispersion d’un matériau polymère ou d’une substance de noyau, respectivement, dans une fluide à haute pression contenant un fluide supercritique et un solvant ajouté, par l’application d’une contrainte de cisaillement de 1 Pa ou plus et une étape d’expulsion par pulvérisation du fluide à haute pression contenant ledit fluide supercritique et ledit solvant ajouté dans un mauvais solvant pour produire ainsi une expansion rapide. Le procédé peut être utilisé de manière appropriée pour préparer des particules fines composites ayant une taille uniforme et de quelques micromètres ou moins, de préférence une taille nanométrique (à savoir de 1 µm ou moins).
PCT/JP2005/021753 2004-11-29 2005-11-21 Procede de preparation de particules fines composites WO2006057374A1 (fr)

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JP2006547886A JPWO2006057374A1 (ja) 2004-11-29 2005-11-21 複合微粒子の製造方法
EP05809275A EP1842586A1 (fr) 2004-11-29 2005-11-21 Procede de preparation de particules fines composites
US11/791,578 US20080274275A1 (en) 2004-11-29 2005-11-21 Method For Preparing Composite Fine Particles
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WO2009063574A1 (fr) * 2007-11-14 2009-05-22 Nikkiso Co., Ltd. Procédé d'atomisation
WO2009049230A3 (fr) * 2007-10-10 2009-06-11 Univ Kansas Matériaux à base de microsphères avec contrôle spatial 3d et temporel prédéfini de biomatériaux, de porosité et/ou de signaux bioactifs
JP2010051850A (ja) * 2008-08-26 2010-03-11 Denso Corp 成膜装置およびそれを用いた成膜方法
JP2011115778A (ja) * 2009-09-15 2011-06-16 Sanyo Chem Ind Ltd 分散液の製造方法
JP2011162416A (ja) * 2010-02-12 2011-08-25 Sumitomo Osaka Cement Co Ltd 集合体粒子の製造方法
US8188212B2 (en) 2008-03-10 2012-05-29 Nikkiso Co., Ltd. Method of enhancing conductivity of conductive polymer product
JP2017128462A (ja) * 2016-01-19 2017-07-27 太平洋セメント株式会社 チタンニオブ酸化物の製造方法、及びこれから得られるチタンニオブ酸化物を用いたチタンニオブ酸化物負極活物質の製造方法
US20200330940A1 (en) * 2017-11-07 2020-10-22 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Mixing apparatus

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ITRM20110195A1 (it) * 2011-04-18 2011-07-18 Galdi Maria Rosa Sistemi attivi a base di pla per la realzzazione di imballaggi rigidi semirigidi e flessibili attvi e biodegradabili
TW201247225A (en) * 2011-05-17 2012-12-01 Univ Nat Chiao Tung Drug carrier with thermal sensitivity, manufacturing method thereof, and use of the same as NMR contrast agent
EP2853104B1 (fr) * 2012-05-23 2018-01-10 Nec Corporation Procédé et système pour la prise en charge de la recherche de grappes synchronisées de stations mobiles dans un réseau de communication sans fil
CN105023773B (zh) * 2014-04-25 2017-09-29 三菱电机株式会社 Ag－氧化物类电触点材料、其制造方法及制造装置、以及断路器及电磁接触器
JP5932120B1 (ja) * 2015-08-21 2016-06-08 恵和興業株式会社 懸濁液の製造装置及びその製造方法
KR101634314B1 (ko) * 2015-10-22 2016-06-30 한방약초힐링 농업회사법인주식회사 식물성 오메가-3 함유 기능성 미세분말 제조방법
CN110115952B (zh) * 2018-02-05 2021-10-15 绍兴吉能纳米科技有限公司 一种可使用低温液化气体的高压均质方法
CN111389315A (zh) * 2020-03-27 2020-07-10 南京芬之怡生物科技有限公司 一种绿色除异净化剂及其制备方法
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CN113134328B (zh) * 2021-04-23 2021-11-23 西南石油大学 一种非均质调控用聚合物微球及其制备方法
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JP2004503603A (ja) * 2000-07-19 2004-02-05 セパレックス マイクロカプセルの形で細かい固形微粒子をカプセルに入れるための方法
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WO2009049230A3 (fr) * 2007-10-10 2009-06-11 Univ Kansas Matériaux à base de microsphères avec contrôle spatial 3d et temporel prédéfini de biomatériaux, de porosité et/ou de signaux bioactifs
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WO2009063574A1 (fr) * 2007-11-14 2009-05-22 Nikkiso Co., Ltd. Procédé d'atomisation
JP2009119363A (ja) * 2007-11-14 2009-06-04 Nikkiso Co Ltd 微粒子化方法
US8460401B2 (en) 2007-11-14 2013-06-11 Nikkiso Co., Ltd. Method of atomization
US8188212B2 (en) 2008-03-10 2012-05-29 Nikkiso Co., Ltd. Method of enhancing conductivity of conductive polymer product
JP2010051850A (ja) * 2008-08-26 2010-03-11 Denso Corp 成膜装置およびそれを用いた成膜方法
JP2011115778A (ja) * 2009-09-15 2011-06-16 Sanyo Chem Ind Ltd 分散液の製造方法
JP2011162416A (ja) * 2010-02-12 2011-08-25 Sumitomo Osaka Cement Co Ltd 集合体粒子の製造方法
JP2017128462A (ja) * 2016-01-19 2017-07-27 太平洋セメント株式会社 チタンニオブ酸化物の製造方法、及びこれから得られるチタンニオブ酸化物を用いたチタンニオブ酸化物負極活物質の製造方法
US20200330940A1 (en) * 2017-11-07 2020-10-22 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Mixing apparatus
US11931709B2 (en) * 2017-11-07 2024-03-19 Kobe Steel, Ltd. Apparatus for mixing materials dissolved in a high-pressure working fluid

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AU2005308133B2 (en) 2008-10-16
EP1842586A1 (fr) 2007-10-10
KR100880117B1 (ko) 2009-01-23
US20080274275A1 (en) 2008-11-06
CN100556531C (zh) 2009-11-04
AU2005308133A1 (en) 2006-06-01
CN101068615A (zh) 2007-11-07
KR20070086857A (ko) 2007-08-27

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